CN102459700B - Alkalescence thin inorganic anti-corrosion coating for metal substrates - Google Patents

Abstract

This application discloses can not carry out phosphorylation pretreatment be applied directly to metal surface and to described surface provide notable antiseptic property neutrality to basic mineral transformation coating compound.Described transformation coating compound preferably has the pH of about 6 to 11, the pH of more preferably 8 to 10.In one embodiment, described coating composition includes at least one element from the Group IVB in the periodic table of elements, and optionally, at least one is from the element of the VB race in the periodic table of elements, and organic polymer.Being preferably based on total drying solid coating weight, described coating composition includes that at least one of 9 73 weight % is from the element of the Group IVB in the periodic table of elements.In another embodiment, described transformation coating compound comprises at least one element from the Group IVB in the periodic table of elements, chromium source, and organic polymer.Being preferably based on total drying solid coating weight, described coating composition includes that at least one of 9 73 weight % is from the element of the Group IVB in the periodic table of elements.Described transformation coating compound is to be dried coating on the spot and create the unique form of continuous inorganic phase after drying, is scattered here and there described organic polymer with the form of discrete polymer spheres in continuous inorganic phase.Described coating composition is of many uses, and can allow to add multiple organic polymer, and described organic polymer can be added directly in described coating composition, therefore eliminates multistep coating procedure.

Description

Alkalescence thin inorganic anti-corrosion coating for metal substrates

Related application

The application is the part continuity of earlier application PCT/US2009/044504, the international application of described earlier application Date is on May 19th, 2009, and it require that the power of U.S. Provisional Application No. 61/054,363 filed in 19 days Mays in 2008 Benefit.

Technical field

Present invention relates generally to the anticorrosion of metal substrates, relate more specifically to neutral to alkalescence thin inorganic on the spot Be dried coating composition, its can not carry out such as phosphating solution (phosphatizing solution) pretreatment and It is directly applied on metal substrates, and metal substrates is provided the antiseptic property of improvement.When being dried on the spot, the present invention On the spot be dried coating additionally provide uniqueness comprise continuous print inorganic phase and the form of discontinuous scattered polymer phase.

Background technology

Untreated metal surface be corroded can cause described surface oxidisation, die down, variable color and rupturing.Therefore, the most logical Cross and various surface activity is weakened and metal substrates is processed by more corrosion resistant method.It addition, metal surface connects down Often it is coated with dicoration or extra protective coating such as resinous coat, priming paint, paint and other surface treatment. The preliminary treatment of metal surface often includes metal tripolyphosphate salt treatment, then carries out rinsing containing chromium.

It is carried out surface process and applies the metal object of coating and can be divided into following a few class.In some commercial Application In, described metal is formed as 3-dimensional object, afterwards, can carry out surface process and/or apply the combination in any of coating.Second In class commercial Application, when described metal is flat form, it is generally rolled rolling, and described metal carries out table before formation Face processes and/or applies coating.Owing to this apoplexy due to endogenous wind exists many coating application, it is desirable to there is special character to promote to wind and become Shape operates.For coating such as organic passivation thing, there is high rigidity and Gao Nai retardance desirable to promote that winding is probably, But, traditional high hardness spray coating often has poor forming characteristic, therefore, the integrity of coating and its corrosion resistance final The operation that will be formed is damaged.It is desirable for providing the coating having high rigidity and good forming characteristic concurrently.

It will be useful for developing corrosion-resistant finishes compositions that is inorganic and that can use under the conditions of neutrality or alkalescence 's.The coating composition that other cosmetic surface treatments that offer will not use before hindering is continuing with also is important 's.Permitted the coating such as organic passivation coating having used Cr VI to be used for metal, because Cr VI has suppression The ability of corrosion.But due to the consideration in terms of environment, Cr VI the most increasingly lacks market.Along with the progress in epoch, Find there is bigger purposes containing chromic coating because its for Cr VI series products on the impact of environment more Low.In many cases, such change all can be along with the decline of corrosion resistance.Therefore, the performance improving coating is the most resistance to Corrosivity is the most desired.Any coating is such as just as by this based on chromic coating.Improve and be not based on six The coating of valency chromium, such as those performance based on trivalent chromium or non-chromium type coating such as corrosion resistances will be more desired.Bag It is also less desirable that coating containing chromium leaches chromium to environment.

Summary of the invention

Generally, the invention provides and can not carry out phosphorylation pretreatment and be applied directly on metal surface and carry Neutrality or alkalescence inorganic coating compositions for notable antiseptic property.When being dried on the spot, the coating of the present invention additionally provides The form of the phase of two unique differences.Described first phase is continuous print inorganic phase, and it is derived from water-soluble inorganic component.Described Two-phase is dispersion phase, and it comprises the polymeric dispersions being in described first phase.This form provides multiple desired coating Attribute.Such attribute includes the good forming characteristic despite high apparent hardness, to metal and alloy such as based on ferrum, zinc With the prominent adhesiveness of those of aluminum, and height chemical-resistant and corrosion resistance.Comprise the present invention's of chromium further Embodiment is not easy to leach chromium, and demonstrates, relative to traditional chromium series products, the corrosion resistance being remarkably reinforced.

The coating composition prepared according to the present invention preferably has the pH of about 6-11, more preferably 8-10.An embodiment party In formula, the coating composition of the present invention comprises at least one from Group IVB transition metal source in the periodic table of elements, this transition Metallic element i.e. zirconium, titanium and hafnium, and optionally, at least one is from VB group 4 transition metal element source in the periodic table of elements, should Transition metal i.e. vanadium, niobium and tantalum.Preferably, described coating composition includes based on total drying solid coating weight 9-73 weight At least one of amount % is from the element of periodic table of elements Group IVB.Preferably Group IVB element is zirconium, preferably with zirconium carbonate ammonium Form provide.Preferably VB race element is vanadium, with V₂O₅Form provide.Described coating composition also includes organic polymer, Wherein said organic polymer active solid percentage by weight based on total drying solid coating weight is 1-75%.

In another embodiment, the coating composition of the present invention comprises at least one from IVB in the periodic table of elements Group 4 transition metal element source, this transition metal i.e. zirconium, titanium and hafnium, and chromium source.Preferably, described coating composition includes base In at least one of total drying solid coating weight 9-73 weight % from the element of periodic table of elements Group IVB.Preferably Group IVB Element is zirconium, preferably provides with the form of zirconium carbonate ammonium.In this embodiment, described coating composition includes chromium source, example Such as chromic acid.Described coating composition also includes organic polymer, and wherein said organic polymer active solid is based on total dry The percentage by weight of dry solid cladding weight is 1-75%.

Coating composition according to the present invention is to be dried conversion coating on the spot.Described coating is because it can allow to add respectively Therefore plant organic polymer is the most multiduty, and described organic polymer can be added directly in coating composition, therefore Eliminating multi-step coating procedure, suitable resinous polymer is can be dispersed or dissolved in described inorganic aqueous coating composition Those.Additionally, described coating shows significant formability and hardness.As a kind of conversion coating, this term is in ability It is known that the component in coating composition is reacted with metal substrates during coating in territory, to produce the final painting being dried on the spot Layer.

By the detailed description to preferred implementation, the these and other feature of the present invention and advantage are for this area For technical staff the most obvious.The accompanying drawing of adjoint described detailed description is as described below.

Accompanying drawing explanation

Figure 1A is the photo of the dark ground scanning transmission electron microscope of the chromium type coating prepared according to the present invention；

Figure 1B is the bigger enlarged drawing of Figure 1A coating；

Fig. 2 A is the photo of the dark ground scanning transmission electron microscope of the non-chromium type coating prepared according to the present invention；

Fig. 2 B is the bigger enlarged drawing of Fig. 2 A coating；

Fig. 3 is the photo of the dark ground scanning transmission electron microscope of the traditional commerce chromium type coating do not prepared according to the present invention.

Detailed description of the invention

It is an object of the invention to process naked metal surface, the naked metal surface meaning is that described metal surface does not use and appoints What metal phosphate solution, carried out pretreatment containing chromium rinsing liquid or arbitrarily other Passivation Treatment.Have benefited from the inventive method Metal surface include steel, cold-rolled steel, hot-rolled steel, rustless steel, aluminum, be coated with zinc metal or kirsite steel such as electrolytic zinc-coated steel sheet, galvalumeZinc-iron alloy (galvanneal) and electro-galvanized steel.

Preferably, before processing according to the present invention, the most cleaned mistake in described metal surface and degreasing.Gold The cleaning of metal surface is to it is known in the art that and can include alkalescence or strong alkaline cleaner.Two kinds of alkaline cleaners Example includes ParcoCleaner ZX-1 and ParcoCleaner 315, both derives from Henkel Surface Technologies.Cleaning preferably rinsed with water after surface before processing according to the present invention.

In one embodiment, the corrosion-inhibiting coating of the present invention includes at least one Group IVB element and at least one VB race Element mixture in deionized water, its pH is about 6-11, and more preferably pH is 8-10.The pH of compositions is maintained at this scope Coating processes is carried out being important.In one embodiment, based on composition total weight, Group IVB element preferably with About 1 to 7 weight %, more preferably from about 2-5 weight %, the amount of most preferably 3-5 weight % exists.Coating composition can include based on Any subrange between 1-7 weight % of gross weight.In this embodiment, based on composition total weight, in compositions VB race element is preferably with about 0.20-2.00 weight %, and the amount of more preferably from about 0.40-1.00 weight % exists.Described coating is permissible Including any subrange between 0.20-2.00 weight % based on gross weight.Preferably, described coating composition is zirconium and vanadium Mixture.One of zirconium preferably originates and is known as Bacote 20Zirconium carbonate ammonium, derive from Flemington New The MEI of Jersey.According to the document from MEI, Bacote 20It is the transparent basic aqueous solution of stable zirconium carbonate ammonium, its Zirconium polymer containing anionic hydroxyl group.It provide the ZrO of about 20%w/w₂.It is as in paper and paper-board applications Cross-linking agent sell.Preferably VB race element is with V₂O₅The vanadium that form provides.Optionally, this coating can further allow for Add polytype organic coating resinous polymer, including, it is only for example: epoxy resin, polyvinyl dichloride, acrylic acid Resinoid, methacrylate-based resin, styrene resin, urethane dispersion, and polyurethanes divides Prose style free from parallelism alloy.The example of these resinous polymers includes CarbosetCR760, Hauthane HD-2120, Hauthane L-2989, Maincote^TMPR-15, Maincote^TMPR-71, Avanse MV-100, Rhoplex AC 337N and Alberdingk-Boley LV-51136 and M-2959.Described coating can also allow for adding for V₂O₅Reducing agent, such as Cysteine, Sn²⁺, ascorbic acid or sulfosuccinic acid.Optionally, people can be always from vanadium oxysulfate or vanadium acetylacetonate V4+ initiates.Optionally, described coating can also include processing aid, such as wax, and it aids in the formability of coating substrate. The addition of these optional reagent is discussed below.

In first embodiment, according to the inorganic coating compositions of the present invention be by by 83.00 weight % go from Son (DI) water and the V of 1.00 weight %₂O₅Bacote 20 with 16.00 weight %Mix and prepare.This content Bacote 20Provide the ZrO accounting for compositions 3.2 weight %₂.The pH of described compositions is about 9.5.Described inorganic coating Being applied on a series of galvanizing by dipping (HDG) plate, described plate is known as ACT HDG plate APR 31893 and U.S.Steel Corp.(USS)GalvalumePlate, wherein uses known wire drawing (draw wire) technique to apply on every square feet The coat weight of 200 milligrams (every 929.03 square centimeters 200 milligrams).GalvalumeIt it is 55% alumin(i)um zinc alloy coating steel disc Trade (brand) name.Once applying, described coating is dried the peak metal temperatures to 210 (98 DEG C) on test board on the spot (PMT)(Peak Metal Temperature).Then described plate is carried out neutral salt spraying (NSS) corrosion test, wherein makes By ASTM B117-03 method, at each time point, multiple plates are tested.In this test, uncoated HDG or USSGalvalumeThe corrosion of 100% is demonstrated in the NSS of 24 hours test.And the respective average corrosion of plate processed Percentage ratio test result is shown below in table 1.

Table 1

Result demonstrates the effectiveness according to the coating composition prepared by the present invention.The coating composition of the present invention exists USS GalvalumeBeing very effective on steel, it is as shown in the table, and it provides the significant antiseptic effect up to 1008 hours. These results and uncoated USS GalvalumeThere is surprising difference, uncoated USS GalvalumeLittle 24 Time the most 100% corrosion.When using HDG substrate, result is also significant, but the most very good.

As previously described, to be that it can easily allow to add organic for the another advantage of coating composition of the present invention Resin is without complicated multi step strategy or applying, to improve antiseptic property further.Only desired resin can be added Enter in described coating composition.In first embodiment that inorganic coating compositions is mixed with organic resin, use poly- Dichloroethylene (PVDC) is as organic resin.The PVDC resin used is Noveon XPD-2903.According to being described in table 2 below Prepare a series of coating composition.

Table 2

Then, drying means on the spot as above is used, with 200 milligrams every square feet (every 929.03 square centimeters 200 milligrams) coat weight each formula is coated to a series of HDG plate and a series of USS GalvalumeOn plate, and It is dried the PMT to 210 (98 DEG C).Use commercially available non-Chromium coating Granocoat342^TM(G342), it obtains From in Henkel, prepare a series of comparison HDG plate and USS GalvalumePlate.Apply G342 according to the manufacturer's instructions.? In first test, plate is carried out NSS test as above, and repeatedly evaluates corrosion percentage ratio at each time point and calculate Meansigma methods.Result is given in Table 3 below, and wherein abbreviation Gal. represents USS GalvalumePlate.

Table 3

Described result demonstrates the antiseptic property of the improvement provided by coating composition of the present invention definitely.Examination USS GalvalumeData on plate, people start to see that all plates of the test by 168 hours all have relative to G342 comparison The improvement of antiseptic property, and along with the increase difference of testing time is consequently increased.After 504 hours, it is coated with according to the present invention The test board covered has the less corrosion of comparison G342 plate 1/18th to 147.After 840 hours, compare G342 plate Extent of corrosion be 28 to 76 times according to coated board of the present invention.After even testing 1200 hours, according to present invention coating Plate only has the corrosion of 3-11%.These results are significant and show the energy of the coating composition prepared according to the present invention Power.Described result also demonstrate polyvinyl dichloride content from 10% increase to 30% pair of final time point time anticorrosion degree have Slight influence.Returning to the data of HDG plate, people are it can be seen that also provide according to the coating of the present invention and be up to relative to G342 The protective effect of the improvement of about 504 hours.The result of HDG plate is not so good as USS GalvalumePlate is notable.Meanwhile, poly-two chloroethenes The effect that alkene content increases seems and at USS GalvalumeThat is seen on plate is contrary.Polyvinyl dichloride content is the highest, On HDG plate, the antiseptic property of coating is the poorest.

Under in a series of corrosion tests, use the formula of table 2 with 200 milligrams every square feet (every 929.03 squares lis Rice 200 milligrams) coat weight by USS GalvalumeOr HDG plate proceeds as described above coating, and on the spot at plate On be dried the PMT to 210 (98 DEG C).Then carry out heap test (Stack Test) to contact with each other in wet environment with simulation Plate.By deionized water of spraying in the coated side of the first plate, the coated side of the second plate is placed in relatively the coating of the first plate Face, then carries out described heap test by the first plate and the second plate holder together.Then the plate of clamping is placed in 100 (38 DEG C) With in the moist test cabinet of 100% humidity.After multiple time points, take out various under the conditions of multiple samples, and determine each From corrosion percentage ratio, result is averaged.Described average result is given in Table 4 below.

Table 4

Described result demonstrate for 10 and 20% resin content for, according to the coating composition of the present invention all Time point all achieve the effect more much better than G342 coating, according to the difference of time point, for G342 16 to 2.2/ One.But, having the coating of 30%PVDC, not compare G342 plate after 1200 hours effective and little through 2016 Time, it demonstrates the extent of corrosion of the about control board of twice.The reason of this difference is unknown.About HDG plate, result shows Control board and according to having less difference between the coating of the present invention.Reach 504 little constantly, described plate all demonstrates aobvious The antiseptic property write.Afterwards, the effect of the coating composition with 20 and 30%PVDC is poorer than G342 plate, and compares 10%PVDC Plate the poorest.

Under in a series of corrosion tests, use the formula of table 2 with 200 milligrams every square feet (every 929.03 squares lis Rice 200 milligrams) coat weight USS coated as described above GalvalumeOr HDG plate, and be dried the most onboard to The PMT of 210 (98 DEG C).Then ASTM method D4585 is used to carry out Cleveland humidity measurement (CHT) over the plates (Cleveland Humidity Test).Result is given in Table 5 below.

Table 5

USS GalvalumeResult prove the present invention coating composition show ratio comparison G342 coating the most very Many, in addition to 1200 hours of 10%PVDC, its result is equal to comparison G342.Described result proves what PVDC measured with will also recognize that Increase the antiseptic property to the coating prepared according to the present invention and there is the most positive effect.Have according to coating of the present invention Seeing similar result on HDG plate, relative to G342, described coating provides the antiseptic property being obviously improved.It addition, PVDC amount Increase seem to improve antiseptic property.

Under in a series of corrosion tests, use the formula of table 2 with 200 milligrams every square feet (every 929.03 squares lis Rice 200 milligrams) coat weight USS coated as described above GalvalumeOr HDG plate, and be dried the most onboard to The PMT of 210 (98 DEG C).Then on a series of plates, carry out Butler water logging (BWI) test.Support each test board and incite somebody to action It is immersed in distillation tank in so that the water of half inch is below each plate, and 3/4ths inches water each plate with On.Then the tank with plate is placed in the moist room being set in 100% humidity and 100 (38 DEG C).In the selected time Point removes plate, and evaluates corrosion percentage ratio.Result is given in Table 6 below.

Table 6

USS GalvalumeResult to prove that the coating prepared according to the present invention provides more obvious than comparison G342 coating More antiseptic property.For G342, antiseptic property improves about 2 times to 10 times.PVDC content is to antiseptic property Impact seem complicated and be nonlinear, high-load demonstrates the efficiency lower than 10-20 weight % content.HDG plate Also show the beneficial effect relative to G342 of the coating according to the present invention.All show relatively according to all plates of present invention coating In the antiseptic property that G342 improves.Again, the impact of PVDC content be complicated and seem 20% PVDC demonstrate Best result.

As it has been described above, the advantage of this coating is that it can easily allow to add organic resin to improve anticorrosion further Performance, without complicated multi step strategy or applying.Only desired resin can be joined in coating composition.In mixing In second embodiment of inorganic coating and organic resin, use thermoplastic styrene AA emulsion, registration CarbosetCR-760, as organic resin.CarbosetCR-760 is the Lubrizol from Cleveland Ohio Advanced Materials, Inc. obtain.CarbosetCR-760 has the solid of about 42 weight %.It is coated with at other In Ceng, CarbosetCR-760 mixes further with PVDC used above.In other preparations, described coating composition is also Including Brazil wax emulsion to improve the formability of coating composition.The Brazil wax emulsion used be from The Michem that the Michelman of Cincinnati Ohio, Inc. obtainLube 160.According to preparing one as described in the following table 7 The coating composition of series.Then, use dry run on the spot as above (every with every square feet upper 175 to 180 milligrams 929.03 square centimeters 175 to 180 milligrams) coat weight each formula is coated in a series of HDG plate and a series of USS GalvalumeOn plate, and the PMT being dried to 210 (98 DEG C).In first corrosion test, plate is carried out as above institute The NSS test stated, and the corrosion percentage ratio of multiple plates is evaluated at each time point.NSS tests the average knot of each time point Fruit is given in Table 8 below.Formula 162B does not has sample to carry out NSS test.Utilize Butler water logging as above test, Ke Li Husband's orchid humidity measurement and heap test, use other plate to evaluate described coating.These test results respectively table 9 below, 10, Be given in 11.

Table 7

Table 8

USS GalvalumeResult prove according to the coating of the present invention all than report in above table 3 The result of G342 coating is more efficient.Only there is CarbosetThe coating of CR-760 is very effective, even if being up to 2016 little constantly.The comparison of formula 162A to 162B shows, in this formula, addition Brazil wax shows and reduces coating Effect as corrosion-inhibiting coating.Described result also shows CarbosetCR-760 with PVDC mixed phase is for being used alone CarbosetCR-760 reduces the effect of described coating composition, but, in mixture, add Brazil wax seem Improve its effect.Do not have coating that HDG sample shows very effective result, and the depositing of Brazil wax or PVDC Only exist Carboset seeming not affectThe performance of CR-760.

Table 9

USS GalvalumeThe result of plate proves, except CarbosetBeyond the mixture of CR-760 Yu PVDC, institute The performance of some coatings is all good than the G342 in table 6.In BWI tests, it is used alone CarbosetPerformance is not had by CR-760 Adverse influence.Contrary with NSS test, CarbosetThe combination of CR-760 Yu PVDC and Brazil wax is in BWI tests Behave oneself best.Again as shown in NSS test result, work as CarbosetWhen CR-760 with PVDC mixes, include cohune Palmitic acid wax has beneficial effect.The result of HDG plate displays that all coatings prepared according to the present invention show all ratios in table 6 G342 is good.It is used alone CarbosetCR-760 obtains relative to addition Brazil wax, PVDC or Brazil wax and PVDC Obtained significantly superior performance.

Table 10

USS GalvalumeAll show with the result of HDG, in the humidity measurement of Cleveland, regardless of substrate, institute The result shown in G342 is compareed during the coating performance of the with good grounds present invention is the best, and all performance is better than table 5.

Table 11

USS GalvalumeResult prove, heap test in, institute the with good grounds present invention coating show the best, And all performance better than table 4 compares the result shown in G342.The result of HDG is different, is used alone CarbosetCR-760 seems to behave oneself best, and the performance of other coatings is poor.Do not appear to coating performance more a lot of than the G342 in table 4.

In another series of tests, in coating, the amount of zirconium carbonate ammonium is change, so that ZrO in coating composition₂Amount Change, and recorded its impact on antiseptic property.Described coating formula is given in table 12 below.It addition, as said above with G342 coats control board.As it has been described above, with the painting of about 200 milligrams every square feet (every 929.03 square centimeters 200 milligrams) Cover weight and described coating is applied to USS GalvalumeOn plate, and the PMT being dried on the spot to 210 (98 DEG C).So After, described plate to be tested in NSS, Butler water logging test and heap are tested, result is given respectively in table 13 below, 14 and 15 Go out.

Table 12

Table 13

Described result proves that the coating of the with good grounds present invention of institute is at least effective as G342, and great majority are all obvious more Add effectively.Described result also confirms that ZrO₂Content increase to 3.20% from 1.20% and significantly increase and prepare according to the present invention The effect of coating.

Table 14

Described result prove again according to the present invention coating performance all than G342 obvious more preferably.Although it addition, not As NSS test in notable, but this result demonstrates ZrO₂The increase of amount enhances described coating in terms of antiseptic property Effect.

Table 15

Described result also confirms that, shows all more preferable than comparison G342 according to the coating of the present invention, but, along with ZrO₂Increasing Add the identical effect increase not as shown in other tests.

In lower series of experiments, according to resin 3272-096 and 3272-103 that preparation described below two kinds is extra, so These resin manufacture of rear use are according to the coating of the present invention, and it is described in detail in table 16 below.

Resin 3272-096

Resin 3272-096 includes that following material is as monomer: acetoacetoxyethyl ethyl ester (AAEM), N-butyl methacrylate, styrene, methyl methacrylate, 2-ethylhexyl acrylate and ADD APT PolySurf HP, it is the mixture of methacrylic acid list and bisphosphate.Monomer total in resin is allocated as follows: 20.00% AAEM, 12.50% n-butyl methacrylate, 15.00% styrene, 27.50% methyl methacrylate, 20.00% 2-ethylhexyl acrylate and 5.00%ADD APT PolySurfHP.At N₂With stirring and heating setpoint under gas Point carries out resin polymerization reaction under conditions of being 80 DEG C.Initially be filled with in reactor is 241.10 grams of DI water, 2.62 grams of Laurels Base ammonium sulfate (Rhodapon L-22EP) and 2.39 grams of ferrous sulfate 0.5%FeSO₄7H₂O(3ppm).At time zero by this Initial reactant is inserted in reactor, and begins heat to set point.After 30 minutes, in reactor, add reaction kind material (reactorseed), described kind material comprises 5.37 grams of DI water, 0.90 gram of nonionic surfactant (Tergitol 15-S- 20), 0.13 gram of ammonium lauryl sulfate (Rhodapon L-22EP), 2.15 grams of n-butyl methacrylate, 2.57 grams of benzene second Alkene, 4.74 grams of methyl methacrylate, 3.48 grams of 2-ethylhexyl acrylates, 3.41 grams of methacrylic acid acetoacetyl oxygen Base ethyl ester (AAEM) and the mixture of 0.85 gram of ADDAPT PolySurf HP, continue to be heated to set point 15 minutes.So After, in container, adding initial initiator charging, it comprises 0.32 gram of HOCH₂SO₂Na, 4.68 grams of DI water, 0.45 gram of tert-butyl group mistake Hydrogen oxide, and 4.54 grams of extra DI water, and temperature is continuously maintained at set point 30 minutes.Then, temperature is being tieed up Hold within the time period of three hours of set point, in container, add monomer and the common material of initiator.Described monomer material altogether It is 106.92 grams of DI water, 17.10 grams of Tergitol 15-S-20,2.49 grams of Rhodapon L-22EP, 40.89 grams of metering systems Acid n-butyl, 48.83 grams of styrene, 89.97 grams of methyl methacrylate, 66.10 grams of 2-ethylhexyl acrylates, 64.77 grams of AAEM and 16.19 grams of ADD APT PolySurf HP.Described initiator material altogether is 0.97 gram of HOCH₂SO₂Na、 14.03 grams of DI water, 1.39 grams of tert-butyl hydroperoxide and extra 13.61 grams of DI water.After three hours, 30 minutes time Between in container, add feed supplement (chaser charge) in section.Described feed supplement is 0.32 gram of HOCH₂SO₂Na, 4.88 grams of DI water, 0.46 gram of tert-butyl hydroperoxide and extra 4.54 grams of DI water.Then set point one hour 30 points is retained the container in Clock.Then start to cool down from set point, continue 2 hours, until temperature is 38 DEG C.Then in container, add buffer agent thing altogether Material.Described buffer agent material altogether is 5.19 grams of ammonium hydroxide (28%) and 18.48 grams of DI water.This resin formation and following in detail In the 3272-103 forming process stated, can be used to replace the phosphate ester-containing that the another kind of ADD APT PolySurf HP is potential Monomer is the Ebecryl 168 from Radcure Corporation.(it is to can be used to replace Tergitol 15-S-20 Secondary alcohol ethoxyl compound) other nonionic surfactant stabilizers be have 15 to 18 other of hydrophilic-lipophilic balance non- Ion stabilizer.The example of these stabilizers includes: other secondary alcohol ethoxyl compounds such as 15-S-15；Mixing of ethoxylate Compound such as Abex2515；Alkyl polyglycol ether such as Emulsogen LCN 118 or 258；Tallow fatty alcohol ethoxylates Thing such as Genapol T 200 and T 250；Isotridecyl alcohol ethoxylate such as Genapol X 158 and X 250；Ten Trialkyl alcohol ethoxylate such as Rhodasurf BC-840；With oleyl alcohol ethoxylate such as Rhoadsurf ON-877.

Resin 3272-103

According to organic coating resin 3272-103 prepared as described below.Resin 3272-103 includes that following material is as list Body: acetoacetoxyethyl ethyl ester (AAEM), n-butyl methacrylate, styrene, methyl methacrylate Base ester, 2-ethylhexyl acrylate and ADDAPT PolySurf HP, it is the mixed of methacrylic acid list and bisphosphate Compound.Monomer total in resin is allocated as follows: 20.00%AAEM, 12.50% n-butyl methacrylate, 15.00% benzene second Alkene, 27.50% methyl methacrylate, 20.00% 2-ethylhexyl acrylate and 5.00%ADD APT PolySurf HP.At N₂Resin polymerization reaction is carried out under conditions of being 80 DEG C with stirring and heating setpoint point under gas.Initially That be filled with in reactor is 286.10 grams of DI water, 2.47 grams of Rhodapon L-22EP.At time zero, this initial reactant is put Enter in reactor, and begin heat to set point.After 30 minutes, adding reaction kind material in reactor, described kind material comprises 5.44 grams of DI water, 0.85 gram of Tergitol 15-S-20,0.12 gram of Rhodapon L-22EP, 2.04 grams of positive fourths of methacrylic acid Base ester, 2.44 grams of styrene, 4.49 grams of methyl methacrylate, 3.30 grams of 2-ethylhexyl acrylates, 3.24 grams of methyl Acrylic acid acetoacetoxyethyl ester (AAEM) and the mixture of 0.81 gram of ADD APT PolySurf HP, continue heating To set point 15 minutes.Then, adding initial initiator charging in container, it comprises 4.79 grams of DI water and 0.21 gram of (NH₄)₂S₂O₈And temperature is continuously maintained at 80 DEG C 30 minutes.Then, in the time period of temperature is maintained set point three hours In, in container, add monomer and the common material of initiator.Described monomer altogether material be 103.36 grams of DI water, 16.15 grams Tergitol 15-S-20,2.35 grams of Rhodapon L-22EP, 38.81 grams of n-butyl methacrylate, 46.34 grams of benzene second Alkene, 85.38 grams of methyl methacrylate, 62.73 grams of 2-ethylhexyl acrylates, 61.47 grams of AAEM and 15.37 grams ADD APT PolySurf HP.Described initiator material altogether is 14.36 grams of DI water and 0.64 gram of (NH₄)₂S₂O₈.After three hours, In container, feed supplement (chaser charge) is added within the time period of 30 minutes.Described feed supplement be 0.35 ascorbic acid, 4.65 Gram DI water, 0.44 gram of tert-butyl hydroperoxide and extra 4.56 grams of DI water and 2.39 grams of ferrous sulfate 0.5% FeSO₄7H₂O(3ppm).Then set point is retained the container in one hour 30 minutes.Then begin to cool down, continue 2 hours, directly It it is 38 DEG C to temperature.Then in container, add buffer agent material altogether.Described buffer agent material altogether is 5.88 grams of ammonium hydroxide (28%) and 18.48 grams of DI water.

Take resin-made as above and with inspection alkali process, impact and the coating of coating are included V for a series of coating₂O₅ Add reducing agent, the beneficial effect of cysteine.For V⁵⁺For, other reducing agents include Sn²⁺, or ascorbic acid or sulfur for amber Amber acid or people can be always from vanadium oxysulfate or the V of vanadium acetylacetonate⁴⁺Initial.Then with every square feet about 200 milli Coating in table 16 is applied on HDG plate by the coat weight of gram (every 929.03 square centimeters 200 milligrams), be then dried to The PMT of 200 or 300 (93 or 149 DEG C), is directly placed into NSS test or first washs then with alkaline cleaner PCI 338 Place into NSS test.Decline with the pretreated antiseptic property of PCI 338 and show that described coating is not alkali-resisting.NSS tests Result is given in table 17 below.

Table 16

Table 17

Described result proves, for resin, and V₂O₅Or the existence of cysteine is all highly profitable for antiseptic power 's.The coating prepared according to the present invention is used to be applied directly on naked metal substrates without any phosphate or except clearly Other pretreatment beyond washing.They can any desired coat weight needed for situation apply, and preferably they are with every square of English Chi 150 to 400 milligrams (every 929.03 square centimeters 150 to 400 milligrams), more preferably every square feet 175 to 300 milligrams (every 929.03 square centimeters 175 to 300 milligrams), most preferably every square feet 175 to 250 milligrams (every 929.03 square centimeter 175 To 250 milligrams) coat weight apply.The coating of the present invention is the conversion coating that is dried on the spot known in the art, and preferably It is dried to 110 to 350 (43 to 177 DEG C), the peak metal temperatures of more preferably 180 to 350 (82 to 177 DEG C), most preferably PMT to 200 to 325 (93 to 163 DEG C).

It is all required for preparing another a series of coating composition to prove Group IVB and VB race element.Time initial according to Component in table 18 below used as described below prepares resin 3340-082.

Table 18

Part A is joined equipped with in 3 liters of flasks of four necks of agitator, condenser, thermocouple and nitrogen inlet.At nitrogen Under atmosphere, content is heated to and maintains 80 DEG C.Mixing portion B1 and B2 is to form the compositions of homogeneous transparent respectively.Will B1 and B2 mixes to form pre-emulsion B.Part C of the pre-emulsion B and 25% of 5% content is filled in described flask And maintain 80 DEG C.After 40 minutes, with constant rate of speed, remaining pre-emulsion B and part C are joined within the time period of 3 hours In described flask, part H is used to rinse the pump that described pre-emulsion adds afterwards so that it is to enter in described flask.By flask Thing is cooled to 70 DEG C, now adds part F in flask.In flask, part D and E is added, so within the time period of 30 minutes After hold the mixture in 70 DEG C 1 hour.Then mixture is cooled to 40 DEG C, now adds part G.Produced emulsion tool There are the solids content of 37.2%, the pH of 6.9, the granularity of 123 nanometers.Then by by the resin 3340-082 of 300 weight portions with The propionic aldehyde of 0.79 weight portion mixes and dihydropyridine functional group is joined in resin to form resin 3340-83.By mixture It is sealed in container, and is placed in the baking oven of 40 DEG C 24 hours, thus form resin 3340-083.Prepare according to such as table 19 below A series of coating composition.Coating composition 164Q is uniquely to prepare according to the present invention, and it includes Group IVB and unit of VB race Element.Coating composition 164R and 164S has each lacked Group IVB or VB race element.Then, with about 200 milligrams every square feet Each coating composition is applied to HDG or Galvalume (Gal) by the coating density of (every 929.03 square centimeters 200 milligrams) On plate, and the peak metal temperatures being dried to 93 DEG C.Then the multiple plates in the case of each are tested at NSS as above In test, and each time point and under the conditions of the average result of multiple samples be reported in table 20 below.

Table 19

Component	164Q	164R	164S
				DI water	62.85	83.95	63.35
Bacote 20	24.0	0.0	24.0
				(NH4)2CO3	0.0	2.9	0.0
V2O5	0.5	0.5	0.0
				Resin 3340-083	12.15	12.15	12.15
Cysteine	0.5	0.5	0.5

Table 20

Result shown in table 20 clearly demonstrate that the beneficial effect of IVB and VB element combinations.When only having a kind of element In the presence of, described coating composition has the antiseptic property of minimum.

In another embodiment, the coating composition prepared according to the present invention comprises inorganic part, described inorganic portion Subpackage containing at least one from the Group IVB transition metal source in the periodic table of elements, this transition metal i.e. zirconium, titanium and Hafnium, and at least one is from the VB race element in the periodic table of elements or chromium source.Described coating composition farther includes organic Polymer.In this embodiment it is preferred that ground, described coating composition includes based on total drying solid coating weight 9 to 73 weight The element of the Group IVB of amount %.Preferably Group IVB element is zirconium, preferably provides with the form of zirconium carbonate ammonium.Preferably In, described coating composition also includes chromium source such as chromic acid or VB race element such as vanadium, niobium or tantalum.According to this embodiment party The coating composition of formula is also to be dried conversion coating on the spot.Described coating also includes at least in various resin organic polymer Kind, it can be added directly in coating composition, therefore eliminates multistep coating procedure.Preferably, organic polymer activity Solid percentage by weight based on total drying solid coating weight is 1% to 75%, more preferably 25% to 73%, most preferably 40% To 70%.The resin organic polymer that can include is various types of, including, it is only for example: epoxy resin, poly-dichloro Ethylene, acrylic resin, methacrylate-based resin, styrene resin, urethane dispersion, and poly-ammonia Carbamate dispersion alloy.The example of these resinous polymers includes CarbosetCR760, Hauthane HD- 2120, Hauthane L-2989, Maincote^TMPR-15, Maincote^TMPR-71, Avanse MV-100, Rhoplex AC 337N and Alberdingk-Boley LV-51136 and M-2959.Described coating can also allow for adding reducing agent, such as Cysteine, Sn²⁺, ascorbic acid or sulfosuccinic acid and their oxidation product.Optionally, described coating composition is all right Including processing aid, such as wax, it aids in the formability of coating substrate.The addition of these optional reagent is as begged for above Opinion.As conversion coating, this term is the component and metal bottom that it known in the art, in coating composition during coating processing Thing reacts, thus produces and final be dried coating on the spot.

The coating composition prepared according to the present invention create there is the unique form be dried coating on the spot.Produced by just Be dried coating morphology and have biphase, unexpectedly, the inorganic part of described coating composition is continuous phase, and discontinuous phase Contain organic polymer.This is contrary with traditional coating and is unforeseeable.Prepare a series of according to the present invention Chromium type coating compositions, and prepare a series of comparative coatings compositions according to the formula provided in table 21 below.By in mixing Lower component is prepared described coating composition so that listed order is added together.After blending and in experiment as described below Before middle use, by aging for all compositionss 24 hours.In these embodiments, Bacote20 serve as Group IVB element source.Have Machine polymer active solid percentage by weight based on total drying solid coating weight is preferably 1% to 75%, more preferably 25% to 73%, most preferably 40% to 70%.Effective organic polymer is described in embodiment before. The organic polymer part of the most all compositionss is all Styrene-acrylic copolymer latex Carboset CR760.Laser light scattering is used to measure described breast by being derived from the Zetasizer 3000HSA of Malvern Instruments The granularity of glue.Particle mean size is 111 nanometers, and its scope is from 62 to 116 nanometers.Based on compositions 21A and 21B active coating solid Chromium content identical with the chromium content of compositions 21C and 21D.In compositions 21B and 21D, comparing embodiment, do not use Bacote20；But use ammonia to add by BacoteThe 20 ammonium content calculated.Compositions 21A and 21B are jonquilleous, in face On color consistent with chromic characteristic color.By contrast, compositions 21C and 21D including reducing agent ascorbic acid are green palm fibres Color, consistent with the characteristic color of mainly trivalent chromium compositions.Embodiment 21A has based on total dry coat solid 44% Emulsion polymer active solid percentage by weight, and this ratio is 41% in embodiment 21C.For embodiment 21A, It is 37.00% that Group IVB element accounts for total percentage by weight being dried coat solid, is 34.50% for 21C.

Table 21

Use the another kind of acrylic latex polymer Avanse from Rohm and HaasMV100 is as organic polymer Thing prepares another a series of coating.By preparing compositions again so that component is mixed by the order in table 22, then make With front by aging for each compositions 24 hours.The organic polymer part of the most all compositionss is all latex AvanseMV100.Laser light scattering is used to measure by being derived from the Zetasizer3000HSA of Malvern Instruments The granularity of described latex.Particle mean size is 137 nanometers, and its scope is from 90 to 207 nanometers.It is coated with based on compositions 22A and 22B activity The chromium content of layer solid is identical with the chromium content of compositions 22C and 22D.In compositions 22B and 22D, comparing embodiment, do not make Use Bacote20；But use ammonia to add by BacoteThe 20 ammonium content calculated.Compositions 22A and 22B are jonquilleous, In color consistent with chromic characteristic color.By contrast, compositions 22C and 22D including reducing agent ascorbic acid are green Brown, consistent with the characteristic color of mainly trivalent chromium compositions.Embodiment 22E is that the non-chromium class prepared according to the present invention is real Execute example.This embodiment be inorganic part include at least one from the element of Group IVB in the periodic table of elements and at least one from The embodiment of the element of VB race in the periodic table of elements.It includes AvanseMV100 is as organic polymer.Embodiment 22A has Have based on total emulsion polymer active solid percentage by weight being dried coat solid 67%, and this ratio is in embodiment 22C It is 65%, is 65.9% in 22E.For embodiment 22A, Group IVB element accounts for total weight percent being dried coat solid Ratio is 21.40%, is 20.50% for 22C, and it is 20.80% for 22E.

Table 22

Use and be derived from the business Cr VI class organic coating solution P3000B of Henkel Corporation as comparing Example 23.

In embodiment 24, by wire drawing bar (wire drawbar), coating composition 21A is applied to the aluminium sheet of cleaning On, and the PMT being dried to 93 DEG C, to provide the dry coating weight of 150 ± 25 millis gram/ft.Then in described painting Au film coating and platinum thin layer is applied, to promote crosscutting (cross-sectioning) on the metal covered.Then, focused ion bundle is used It is crosscutting, the thinnest to produce coating substrate cross section section.Then, by dark ground scanning transmission electron microscope to described horizontal stroke Cross section carries out feature analysis.The image institute that the new form such as this technique of the coating composition prepared according to the present invention is obtained Showing, display is in figs. 1 a and 1b.In the process, relatively bright in image regional correlation reflects combination in relatively dark region The average atom number (Z) of each composition in thing.Bright area represents the existence of the composition of higher average Z, and dark areas represents relatively low flat All compositions of Z.Carry out Energy Dispersive X-ray analysis elementary composition with check in these regions.Described analysis shows continuous phase It it is the inorganic phase comprising chromium, zirconium and oxygen.Described technique relates to the transmission by dry coating slice, and described dry coating comprises Continuously and dispersed substance phase, this significant difference on average Z.As result, it is provided that three-dimensional situation image and showing The form that the present invention is new.After the coating of embodiment 21A applied is dried, zirconium carbonate ammonium (Bacote20) residue tribute Dedicate bright area to.Acrylic latex polymer, it, in large quantities based on carbon and oxygen, will be represented by dark areas.In a slice with not The dark areas of image is created with the polymer spheres that the degree of depth is overlapping.As shown in it, it should be noted that and the invention provides tool There is the coating of continuous inorganic matrix, inside described continuous inorganic matrix, there is discrete scattered polymer spheres.In image from The size of the polymer spheres dissipated is consistent with the measurement granularity of acrylic based emulsion in embodiment 21.The elongation attribution of polymer spheres The blockage effect of period it is dried in composite construction.Observe Figure 1A, platinum/gold cap as indicated by 10, coating composition 21A as indicated at 20, As shown at 22, continuous print inorganic phase is as indicated at 24 for dispersed polymeres spheroid.Substrate aluminum is as represented at 30.Figure 1B be Figure 1A region more Big enlarged drawing and clearly demonstrate continuous inorganic phase 24 and dispersed polymeres spheroid 22.Clearly, it is different from the present invention In expection, polymer emulsion does not coalesces, and is saved in continuous print inorganic phase with dispersion phase.

In embodiment 25, by wire drawing bar (wire drawbar) by compositions 22E, the non-chromium embodiment of the present invention, It is applied to the galvalume of cleaningOn plate, and the PMT being dried to 93 DEG C, to provide 200 ± 25 millis gram/ft It is dried coating weight.Then, use focused ion bundle by crosscutting, to produce thin section, by embodiment 24 for the metal of coating Described in dark ground scanning transmission electron microscope it is carried out characterization.Which demonstrate the characteristic morphology that the present invention is new, have a large amount of The continuous inorganic phase of discrete dispersin polymerization body phase.Carry out Energy Dispersive X-ray analysis described continuously and in dispersion phase with inspection Elementary composition.Again, described continuous phase is to comprise the inorganic phase of zirconium, vanadium and oxygen.Gathering in coating 22E observed Compound sphere size is consistent with the measurement granularity of latex used in embodiment 22E preparation.Relative to embodiment 24, people observe To coat inside higher polymer drops body density, itself and the difference of acrylic acid content in embodiment 21A and embodiment 22E preparation Unanimously.Result shows in Figures 2 A and 2 B, and Fig. 2 B is the bigger enlarged drawing in region shown in Fig. 2 A.Platinum/gold cap as indicated at 60, is coated with Layer composition 50 includes polymer spheres 54 and continuous print inorganic phase 52, and substrate is as shown at 40.

In embodiment 26, by wire drawing bar (wire drawbar), comparing embodiment 23 is applied to the aluminium sheet of cleaning On, and the PMT being dried to 93 DEG C, to provide the dry coating weight of 150 ± 25 millis gram/ft.Then, focusing is used It is crosscutting that ion beam will coat metal, to produce thin section, by the dark ground scanning transmission electron microscope pair described in embodiment 24 It carries out characterization.The new form of the coating prepared according to the present invention by the picture specification that this technique obtains is in business Chromium type coating does not exists.Observed is the thin film comprising the continuous organic facies produced by coalesced polymer, and this is tradition The feature of polymer coating.Carry out Energy Dispersive X-ray analysis elementary composition with check in described continuous phase.In figure 3, As indicated at 80, the polymer of coalescence is as shown in 90, and platinum/gold cap is as shown in 100 for substrate.

As it appears from the above, a shortcoming of current chromium type coating compositions is to be applied on substrate later chromium from painting at it The trend leached in layer composition.Therefore, will enter with the comparison sample in embodiment 27 according to the leaching of embodiments of the invention Row contrast.In embodiment 27, it is applied to clean by each Chromium coating compositions of embodiment 21 and 22 by wire drawing bar Electro-galvanized steel (HDG) and GalvalumeOn plate, and the PMT being dried to 93 DEG C.Dry coating weight on HDG plate is 175 ± 25 millis gram/ft.GalvalumeDry coating weight on plate is 150 ± 25 millis gram/ft.Coating Afterwards, described plate is carried out test program and leach the trend of chromium with characterization the most when exposed to water.Plate is dipped in 1.5 liters In warm deionized water at 50 DEG C 30 seconds, afterwards with cold water wash they 30 seconds and be dried.Plate is being carried out test program Before and after, use 2501 types that Cianflone Scientific Instruments Corporation manufactures Portspec X-ray spectrograph measures the chromium content of coated board.Calculate the difference of chromium content after immersion program.Chromium loses Percent levels according to following corresponding to 0 to 5 numeral: 0 is ＜ 5%；1 is 5% to 19.99%；2 be 20.00% to 39.99%；3 is 40.00% to 59.99%；4 is 60.00% to 79.99%；5 is 80.00% to 100.00%.Result shows In table 28 below.Described result shows several obvious trend.First, the coating prepared according to the present invention does not show from respectively Individual substrate significantly leaches.Second, the most all comparing embodiments all demonstrate and leach from all substrates.3rd, main If trivalent chromium comparing embodiment demonstrates the leaching more significantly more than the comparing embodiment of mainly sexavalence.Finally, all ratios The performance on HDG of the relatively compositions is all better than at GalvalumeOn.

Table 28

In embodiment 29, by wire drawing bar by compositions 21A, 21C and compare commercial embodiment 23 be applied to cleaning Electro-galvanized steel and GalvalumeOn plate, and the PMT being dried to 93 DEG C.The dry coating weight obtained on HDG is 200 ± 25 millis gram/ft, at GalvalumeObtain on plate is 150 ± 25 millis gram/ft.Then, will be every 3 copy boards of individual compositions are placed in according in the neutral salt spray test of ASTM-B117-07A, and at regular intervals Check.Under each is spaced, corrosion is graded with % surface oxidisation.For first 168 hours that salt spray exposes, every 24 little Shi Jinhang once grades, and within the most every 168 hours, once grades.Record three copy board respective % surface oxidisation reach or Exposure duration hourage more than 10% and 25% limit.The average open-assembly time meeting or exceeding definition limit is summarised in following table In 29.Result clearly illustrates that the coating composition prepared according to the present invention is substantially better than the business chromium type coating combination of test Thing.It addition, at GalvalumeOn all performances significantly better than on HDG.

Table 29

In embodiment 30, the coating composition of embodiment 22 is contrasted with comparing embodiment 23.By wire drawing bar Embodiment 22A, 22C and comparing embodiment 23 are applied to electro-galvanized steel and the Galvalume of cleaningOn plate, and it is dried To the PMT of 93 DEG C.The dry coating weight obtained on HDG is 200 ± 25 millis gram/ft, at GalvalumePlate Upper acquisition is 150 ± 25 millis gram/ft.Then, 3 copy boards of each compositions are placed in neutral salt spray test In, and in addition to 192 hours and 144 hours the two time intervals, during whole test with the time of 168 hours between Every checking.Under each is spaced, corrosion is graded with % surface oxidisation.Record three copy board respective % surface oxidisation Meet or exceed the exposure duration hourage of 3% limit.Average open-assembly time is summarised in table 30 below.Again, the present invention The performance having performed more than comparing embodiment, and at GalvalumeOn all performances be all better than on HDG.

Table 30

More than inventing and be described according to relevant statutory standards, this description is exemplary rather than substantially Limit.Conversion and modification to disclosed embodiment may be apparent to those skilled in the art, and Within it also falls into the scope of the present invention.Therefore, law give protection scope of the present invention only can be by the appended right of research Require to determine.

Claims (19)

1. The corrosion-inhibiting coating being dried the most on the spot, described painting is deposited upon on metal substrates and has and includes following form:

   The continuous phase being made up of inorganic phase, based on total drying solid coating weight, described inorganic phase is substantially by 9-73 weight % At least one elementary composition from the Group IVB in the periodic table of elements；With

   The discontinuous phase being made up of organic facies, described organic facies is substantially by the active solid group of at least one organic polymer Becoming, based on total drying solid coating weight, the active solid of at least one organic polymer described is deposited with the amount of 1-75 weight % Being in described coating, the active solid of at least one organic polymer described is dispersed in the form of discrete polymer spheres In described continuous print inorganic phase, and at least one organic polymer wherein said is selected from polyvinyl dichloride resin, acrylic compounds Resin, methacrylate-based resin, styrene resin, and their mixture.
2. 2. the corrosion-inhibiting coating being dried the most on the spot as described in claim 1, wherein said Group IVB element include titanium, zirconium, hafnium or its Mixture.
3. 3. the corrosion-inhibiting coating being dried the most on the spot, wherein, based on total drying solid coating weight, described The percentage by weight of organic polymer active solid is 25-73 weight %.
4. 4. the corrosion-inhibiting coating being dried the most on the spot, wherein, based on total drying solid coating weight, described The percentage by weight of organic polymer active solid is 40-70 weight %.
5. The corrosion-inhibiting coating being dried the most on the spot, described painting is deposited upon on metal substrates and has and includes following form:

   The continuous phase being made up of inorganic phase, based on total drying solid coating weight, described inorganic phase is substantially by 9-73 weight % At least one elementary composition from the Group IVB in the periodic table of elements, wherein, described continuous inorganic phase farther includes at least A kind of element of the VB race in the periodic table of elements；With

   The discontinuous phase being made up of organic facies, described organic facies is substantially by the active solid group of at least one organic polymer Becoming, based on total drying solid coating weight, the active solid of at least one organic polymer described is deposited with the amount of 1-75 weight % Being in described coating, the active solid of at least one organic polymer described is dispersed in the form of discrete polymer spheres In described continuous print inorganic phase, and at least one organic polymer wherein said is selected from polyvinyl dichloride resin, acrylic compounds Resin, methacrylate-based resin, styrene resin, and their mixture；

   The described corrosion-inhibiting coating being dried on the spot comprises further for reducing the reducing agent of described VB race element or its product.
6. 6. the corrosion-inhibiting coating being dried the most on the spot as described in claim 5, wherein, described reducing agent includes cysteine, anti-bad Hematic acid, Sn²⁺, sulfosuccinic acid or their mixture.
7. 7. the corrosion-inhibiting coating being dried the most on the spot as described in claim 5, wherein, described at least one from the periodic table of elements The element of VB race include vanadium.
8. The corrosion-inhibiting coating being dried the most on the spot, described coating is for metal substrates and has and includes following form:

   The continuous print inorganic phase being made up of inorganic phase, described inorganic phase is substantially by being 9-73 based on total drying solid coating weight At least one of weight % forms from element and the chromium source of the Group IVB in the periodic table of elements；With

   The discontinuous phase being made up of organic facies, described organic facies is substantially by the active solid group of at least one organic polymer Becoming, the active solid of at least one organic polymer described is deposited with the amount of 1-73 weight % based on total drying solid coating weight , the active solid of at least one organic polymer described is dispersed in described the most inorganic with the form of discrete polymer spheres Xiang Zhong, and at least one organic polymer wherein said is selected from polyvinyl dichloride resin, acrylic resin, methacrylic acid Esters resin, styrene resin, and their mixture.
9. 9. the corrosion-inhibiting coating being dried the most on the spot as described in claim 8, wherein, described Group IVB element include titanium, zirconium, hafnium or Their mixture.
10. 10. the corrosion-inhibiting coating being dried the most on the spot, wherein, based on total drying solid coating weight, described The percentage by weight of organic polymer active solid is 25-73 weight %.
11. 11. corrosion-inhibiting coatings being dried the most on the spot, wherein, based on total drying solid coating weight, described The percentage by weight of organic polymer active solid is 40-70 weight %.
12. 12. corrosion-inhibiting coatings being dried on the spot, described coating is for metal substrates and has and includes following form:

    The continuous print inorganic phase being made up of inorganic phase, described inorganic phase is substantially by being 9-73 based on total drying solid coating weight At least one of weight % forms from element and the chromium source of the Group IVB in the periodic table of elements；With

    The discontinuous phase being made up of organic facies, described organic facies is substantially by the active solid group of at least one organic polymer Becoming, the active solid of at least one organic polymer described is deposited with the amount of 1-73 weight % based on total drying solid coating weight , the active solid of at least one organic polymer described is dispersed in described the most inorganic with the form of discrete polymer spheres Xiang Zhong, and at least one organic polymer wherein said is selected from polyvinyl dichloride resin, acrylic resin, methacrylic acid Esters resin, styrene resin, and their mixture；

    The described corrosion-inhibiting coating being dried on the spot comprises the element of periodic table of elements VB race and further for reducing described VB race The reducing agent of element or its product.
13. 13. corrosion-inhibiting coatings being dried the most on the spot, wherein, described reducing agent includes cysteine, resists Bad hematic acid, Sn²⁺, sulfosuccinic acid or their mixture.
14. 14. anticorrosion transformation coating compounds, described compositions is for metal substrates and includes:

    Continuous phase inorganic part, described inorganic part substantially by based on total drying solid coating weight be 9-73 weight % extremely The element of few a kind of Group IVB in the periodic table of elements and chromium source composition；With

    Discontinuous phase organic moiety, described organic moiety is substantially by being 1-75 weight % based on total drying solid coating weight The active solid composition of at least one organic polymer, the active solid of at least one organic polymer described is with discrete polymerization The form of thing spheroid is dispersed in described inorganic part, and wherein said transformation coating compound has the pH of 6-11, and At least one organic polymer wherein said selected from polyvinyl dichloride resin, acrylic resin, methacrylate-based resin, Styrene resin, and their mixture.
15. 15. anticorrosion transformation coating compounds as described in claim 14, wherein, described Group IVB element includes titanium, zirconium, hafnium Or their mixture.
16. 16. anticorrosion transformation coating compounds as described in claim 14, wherein, based on total drying solid coating weight, institute The percentage by weight stating organic polymer active solid is 25-73 weight %.
17. 17. anticorrosion transformation coating compounds as described in claim 14, wherein, based on total drying solid coating weight, institute The percentage by weight stating organic polymer active solid is 40-70 weight %.
18. 18. anticorrosion transformation coating compounds, described compositions is for metal substrates and includes:

    Continuous phase inorganic part, described inorganic part substantially by based on total drying solid coating weight be 9-73 weight % extremely The element of few a kind of Group IVB in the periodic table of elements and chromium source composition；With

    Discontinuous phase organic moiety, described organic moiety is substantially by being 1-75 weight % based on total drying solid coating weight The active solid composition of at least one organic polymer, the active solid of at least one organic polymer described is with discrete polymerization The form of thing spheroid is dispersed in described inorganic part, and wherein said transformation coating compound has the pH of 6-11, and At least one organic polymer wherein said selected from polyvinyl dichloride resin, acrylic resin, methacrylate-based resin, Styrene resin, and their mixture；

    Described anticorrosion transformation coating compound comprises the element of periodic table of elements VB race and further for reducing described VB race The reducing agent of element or its product.
19. 19. anticorrosion transformation coating compounds as described in claim 18, wherein, described reducing agent includes cysteine, resists Bad hematic acid, Sn²⁺, sulfosuccinic acid or their mixture.